Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer

Abstract

The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer according to the present invention is prepared by copolymerizing 50-90 mol % of ethylene, 1-55 mol % of an aromatic vinyl compound and 1-55 mol % of a vinylnorbornene under a catalyst system consisting of a transition metal compound represented by formula (I) and a cocatalyst, where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium; Cp′ is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 liner alkyl substitutes; an indenyl group; a substituted indenyl group; a fluorenyl group; or a substituted fluorenyl group; Y is a hydrogen or a silyl group of C 1-10 , an alkyl group of C 1-10 , an aryl group of C 1-10 , or a combination thereof; A is an alkyl group of C 1-30 , an alkylamide group of C 1-30 or a derivative of cyclopentadienyl group which is identical to Cp′; and X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.

What is claimed is:  
     
         1 . A method of preparing an ethylene/aromatic vinyl compound/vinylnorbornene terpolymer by copolymerizing 50˜90 mol % of ethylene, 1˜55 mol % of an aromatic vinyl compound and 1˜55 mol % of a vinylnorbornene under a catalyst system consisting of a transition metal compound represented by the following formula (I) and a cocatalyst:  
       
         
           
           
               
               
           
         
         where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;  
         Cp′ is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a tetrahydroindenyl group; a substituted indenyl group; a fluorenyl group; a octahydrofluorenyl group; or a substituted fluorenyl group;  
         Y is a hydrogen or a silyl group of C 1-10 , an alkyl group of C 1-10 , an aryl group of C 1-10 , or a combination thereof;  
         A is an alkyl group of C 1-30 , an alkylamide group of C 1-30  or a derivative of cyclopentadienyl group which is identical to Cp′; and  
         X is selected from the group consisting of a hydrogen atom. a halogen atom. an alkyl group, an aryl group or a diene group.  
       
     
     
         2 . The method of  claim 1 , wherein said cocatalyst is an organometallic compound or a mixture of a non-coordinated Lewis acid and an alkylaluminum compound.  
     
     
         3 . The-method of  claim 2 , wherein said organometallic compound is an alkylaluminoxane or an organoaluminum compound.  
     
     
         4 . The method of  claim 3 , wherein said alkylaluminoxane is methylaluminumoxane (MAO) or a modified methylaluminumoxane (MMAO).  
     
     
         5 . The method of  claim 3 , wherein said organoaluminum compound includes an alkylaluminoxane having a repeating unit of the following formula (II), said alkylaluminoxane including a linear alkylaluminoxane represented by the following formula (III), and a cyclic alkylaluminoxane represented by the following formula (IV):  
       
         
           
           
               
               
           
         
         wherein R is an hydrogen, alkyl group of C 1-5  or aryl group of C 1-6  and may be the same or different from each other, and m and n are an integer of 0˜100.  
       
     
     
         6 . The method of  claim 2 , wherein said non-coordinated Lewis acid is selected from the group consisting of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, ferrocerium tetrakis(pentafluorophenyl)borate, and tris(pentafluorophenyl)borate.  
     
     
         7 . An ethylene/aromatic vinyl compound/vinylnorbornene terpolymer consisting essentially of 50˜90 mol % of ethylene, 1˜55 mol % of aromatic vinyl compound and 1˜55 mol % of vinylnorbornene, which is polymerized under a catalyst system consisting of a transition metal compound represented by the following formula (I) and a cocatalyst:  
       
         
           
           
               
               
           
         
         where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;  
         Cp′ is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a tetrahydroindenyl group; a substituted indenyl group; a fluorenyl group; a octahydrofluorenyl group; or a substituted fluorenyl group;  
         Y is a hydrogen or a silyl group of C 1-10 , an alkyl group of C 1-10 , an aryl group of C 1-10 , or a combination thereof;  
         A is an alkyl group of C 1-30 , an alkylamide group of C 1-30  or a derivative of cyclopentadienyl group which is identical to Cp′; and  
         X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.  
       
     
     
         8 . The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of  claim 7 , in which said vinylnorbornene portion has terminal double bonds.  
     
     
         9 . The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of  claim 7 , wherein said terpolymer shows distinct peaks near 112 and 114 ppm in the  13 C-NMR spectrum due to the terminal double bonds.  
     
     
         10 . The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of  claim 7 , wherein said terpolymer shows stretching bands due to the terminal double bonds of C═C and ═C—H near 1636 and 995 cm −1 , respectively, in the FT-IR spectrum.  
     
     
         11 . The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of  claim 7 , wherein said terpolymer has a weight average molecular weight of at least 5,000.